CN111149239B - Composition for secondary battery electrode - Google Patents
Composition for secondary battery electrode Download PDFInfo
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- CN111149239B CN111149239B CN201880063369.3A CN201880063369A CN111149239B CN 111149239 B CN111149239 B CN 111149239B CN 201880063369 A CN201880063369 A CN 201880063369A CN 111149239 B CN111149239 B CN 111149239B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/38—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a acetal or ketal radical
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The purpose of the present invention is to provide a composition for a secondary battery electrode, which has excellent dispersibility and adhesiveness of an active material, can prevent battery deterioration and failure due to moisture absorption, and can produce a high-capacity secondary battery. The present invention provides a composition for a secondary battery electrode, comprising an active material, a binder and an organic solvent, wherein the binder comprises a polyvinyl acetal resin having an electron-withdrawing group and an electron-donating group having an acid dissociation constant in water of less than 16, the polyvinyl acetal resin having a degree of polymerization of 250 to 800 and a hydroxyl group content of 35 to 70 mol%.
Description
Technical Field
The present invention relates to a composition for a secondary battery electrode, which has excellent dispersibility and adhesiveness of an active material, can prevent deterioration and failure of a battery due to moisture absorption, and can produce a high-capacity secondary battery.
Background
In recent years, with the popularization of portable electronic devices such as a portable video camera and a portable personal computer, the demand for secondary batteries as a power source for mobile use has been increasing. In addition, there is a very high demand for downsizing, weight saving, and high energy density of such secondary batteries.
As described above, as a secondary battery that can be repeatedly charged and discharged, a water-soluble battery such as a lead battery or a nickel-cadmium battery has been mainly used, and although these water-soluble batteries have excellent charge and discharge characteristics, it cannot be said that these water-soluble batteries have characteristics that can be sufficiently satisfied as a portable power source for a portable electronic device in terms of battery weight and energy density.
Accordingly, research and development of lithium secondary batteries using lithium or lithium alloy as a negative electrode have been actively conducted as secondary batteries. The lithium secondary battery has the following excellent characteristics: has high energy density, less self-discharge and light weight.
The electrode of the lithium secondary battery is generally formed as follows: the electrode is formed by kneading an active material and a binder together with a solvent, dispersing the active material to prepare a slurry, and then applying the slurry to a current collector by a doctor blade method or the like, and drying the slurry to prepare a thin film.
In particular, a fluorine-based resin typified by polyvinylidene fluoride (PVDF) is most widely used as a binder for an electrode of a lithium secondary battery.
However, when a fluororesin is used as a binder, a film having flexibility can be produced, but on the other hand, the adhesion between the current collector and the active material is poor, and therefore, there is a possibility that a part or all of the active material may be peeled off and peeled off from the current collector during the battery manufacturing process. In addition, when the battery is charged and discharged, intercalation and deintercalation of lithium ions into the active material are repeated, and the following problems are associated therewith: there is a possibility that the active material may be peeled off from the current collector.
To solve this problem, attempts have also been made to use adhesives other than PVDF. However, when the conventional resin is used, there is a new problem that the resin is decomposed and deteriorated when a voltage is applied to the electrode. When such deterioration of the resin occurs, there is a problem that the charge-discharge capacity is lowered or the electrode is peeled off.
In contrast, patent document 1 describes a binder for nonaqueous secondary batteries, which contains a copolymer of an acid functional group-containing monomer and an amide group-containing monomer.
However, when such a binder is used, the dispersibility of the active material becomes low, and the viscosity of the electrode composition becomes high, so that the time required for filtering the paste becomes long, the process time becomes long, and coating unevenness is likely to occur at the time of coating. Further, since the density of the active material in the electrode is reduced, the capacity of the resulting battery becomes insufficient.
Further, when such a resin is used, the flexibility of the electrode becomes low, and cracks and peeling off from the current collector occur, which causes a problem that the durability of the battery is lowered.
Patent document 2 discloses a composition for a secondary battery positive electrode binder containing predetermined amounts of an aromatic vinyl unit, a nitrile unit, a hydrophilic group unit, and a linear alkylene unit.
However, even when such a composition is used, dispersibility of the active material becomes low, and therefore, the paste filtration takes a long time, the process time becomes long, and uneven coating is likely to occur at the time of coating. In addition, when the electrode composition is prepared in a state of high water content, acid gas may be generated from the inside of the battery due to the influence of moisture, and swelling, ignition, and explosion of the battery may be induced.
Further, since the density of the active material in the electrode is reduced, the capacity of the resulting battery becomes insufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5708872
Patent document 2: japanese patent laid-open No. 2013-179040
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a composition for a secondary battery electrode, which has excellent dispersibility and adhesiveness of an active material, can prevent battery deterioration and failure due to moisture absorption, and can produce a high-capacity secondary battery.
Means for solving the problems
The invention relates to a composition for secondary battery electrode, which contains active material, binder and organic solvent,
the binder contains a polyvinyl acetal resin having an electron-withdrawing group and an electron-donating group having an acid dissociation constant in water of less than 16, and having a degree of polymerization of 250 to 800 and a hydroxyl group content of 35 to 70 mol%.
The present invention is described in detail below.
The inventors have found as a result of intensive studies that: as a binder for forming an electrode of a secondary battery, a polyvinyl acetal resin having a specific electron donating group and electron withdrawing group is used, whereby dispersibility and adhesiveness of an active material are excellent. It was found that in addition: the present invention has been made to solve the above problems, and an object of the present invention is to provide a secondary battery capable of preventing deterioration and failure of a battery due to moisture absorption, and capable of manufacturing a high-capacity secondary battery even when the amount of binder added is small.
The composition for a secondary battery electrode of the present invention contains an active material.
The composition for a secondary battery electrode of the present invention can be used for any electrode of a positive electrode and a negative electrode, and can also be used for both the positive electrode and the negative electrode. Accordingly, as the active material, there are a positive electrode active material and a negative electrode active material.
Examples of the positive electrode active material include lithium-containing composite metal oxides such as lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, ni—co—mn ternary system Li-containing oxide, and ni—co—al ternary system Li-containing oxide. Specifically, for example, liNiO 2 、LiCoO 2 、LiMn 2 O 4 Lithium iron phosphate, and the like.
It should be noted that these may be used alone or in combination of 2 or more.
As the negative electrode active material, for example, materials conventionally used as a negative electrode active material of a secondary battery may be used, and examples thereof include spherical natural graphite, artificial graphite, amorphous carbon, carbon black, and materials obtained by adding different kinds of elements to these components.
The composition for a secondary battery electrode of the present invention preferably contains a conductivity imparting agent (conductivity aid).
Examples of the conductivity imparting agent include carbon materials such as graphite, acetylene black, carbon black, ketjen black, and vapor grown carbon fibers. In particular, acetylene black and carbon black are preferable as the conductivity imparting agent for the positive electrode, and acetylene black and scaly graphite are preferable as the conductivity imparting agent for the negative electrode.
The composition for a secondary battery electrode of the present invention contains a polyvinyl acetal resin. In the present invention, by using a polyvinyl acetal resin as a binder (binder), attractive interaction occurs between the hydroxyl group of the polyvinyl acetal resin and the oxygen atom of the positive electrode active material, and the positive electrode active material is surrounded by the polyvinyl acetal resin. In addition, the interaction between other hydroxyl groups in the same molecule and the conductivity-imparting agent involves attraction, and the distance between the active material and the conductivity-imparting agent can be kept within a specific range. In this way, the active material and the conductivity imparting agent are provided with a characteristic structure at a proper distance, and thus the dispersibility of the active material is greatly improved. In addition, the adhesion to the current collector can be improved as compared with the case of using a resin such as PVDF. Further, the solvent solubility is excellent, and the solvent selection range is wide.
The polyvinyl acetal resin has an electron donating group having an acid dissociation constant in water of less than 16.
In the present invention, the electron conductivity can be improved and the resistance can be suppressed by using the electron donating group in combination with an electron withdrawing group described later.
In the present invention, the "electron donating group" means a functional group having a para effect σp of less than 0 in the substituent constant of hamett (Hammett), and the "electron withdrawing group" means a functional group having a para effect σp of 0 or more.
The electron donating group and the electron withdrawing group do not contain a hydroxyl group or an acetyl group.
The electron donating group has an acid dissociation constant (pKa) in water of less than 16.
By making the pKa smaller than 16, electrons can be easily released. The pKa is preferably less than 12. The pKa is preferably 0.1 or more.
The pKa of the electron donating group may be measured by a potentiometric method or a neutralization titration method.
The bonding position of the electron donating group is not particularly limited, and may be directly bonded to the main chain carbon, or may be bonded via a linking group. In addition, the structure may be bonded to an acetal group. Further, the graft chain having an electron donating group may be bonded to the resin, or the electron donating group may be bonded to the terminal of the resin.
Among them, a structure directly bonded to the main chain carbon and a structure bonded to the main chain carbon via a linking group are preferable.
Examples of the electron donating group include a lower alkoxy group, an ether group, an amino group, an alkylamino group, -S-, and a functional group having a lactam structure. In the present invention, lower alkoxy means straight-chain or branched alkoxy having 1 to 6 carbon atoms.
The electron donating group is preferably a functional group having a lactam structure.
The polyvinyl acetal resin has an electron donating group, so that it is excellent in electrolyte resistance, adhesion to a current collector, and ion conductivity, and there is an advantage in that a high-capacity secondary battery can be produced even when the amount of the binder added is reduced.
Further, the present invention has an advantage that deterioration due to moisture absorption during long-term storage can be prevented and the storage property is excellent.
In the present invention, the lactam structure means a structure having a lactam group.
The lactam group is a group obtained by removing a hydrogen atom or an alkyl group bonded to a nitrogen atom of the lactam compound.
Examples of the lactam compound include caprolactam, N-alkylcaprolactams, pyrrolidones, piperidones, and the like.
Examples of the N-alkylcaprolactams include N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-N-propylcaprolactam, N-N-butylcaprolactam, and N-cyclohexylcaprolactam.
Examples of the pyrrolidone include 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-N-propyl-2-pyrrolidone, N-N-butyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone.
Examples of the piperidones include 2-piperidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, and N-isopropyl-2-piperidone.
The lactam group may be substituted with a substituent such as a halogen atom, a hydroxyl group, a carboxyl group, an amide group, an alkyl ester group, an alkylamide group, a nitro group, or a salt thereof.
The lactam structure is preferably a structure represented by the following formula (1).
In the formula (1), n represents an integer of 1 to 5, R 1 Represents a single bond or a saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms.
When the lactam structure represented by the formula (1) has a structure in which a lactam group is bonded to a main chain via a saturated or unsaturated hydrocarbon, the lactam structure is not easily affected by the main chain via the saturated or unsaturated hydrocarbon. R is as follows 1 Preferably a single bond.
R is as described above 1 Is a single bond or a saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms. As R as above 1 Examples thereof include linear or branched alkylene groups, arylene groups, and the like.
The alkylene group is preferably a linear alkylene group, and preferably an alkylene group having 1 to 6 carbon atoms. Among them, methylene, ethylene, propylene and the like are preferable.
The above-mentioned lactam structure is preferably a three-membered ring to a seven-membered ring, and more preferably has at least 1 cyclic structure selected from the group consisting of a three-membered ring, a four-membered ring, a five-membered ring and a six-membered ring. This can prevent the reaggregation of the active material and the conductive additive by the steric hindrance of the cyclic structure, and can produce a paste with a small rate of change in viscosity with time. N is preferably an integer of 1 to 5, and n is more preferably 1 or 2.
The hydrocarbon constituting the cyclic structure of the lactam structure is preferably unsubstituted or a hydrogen atom is substituted with a saturated hydrocarbon or an unsaturated hydrocarbon having 1 to 10 carbon atoms.
When the hydrogen atom of the hydrocarbon constituting the cyclic structure of the lactam structure is substituted, the hydrogen to be substituted is preferably α hydrogen or β hydrogen.
The saturated hydrocarbon or unsaturated hydrocarbon having 1 to 10 carbon atoms is preferably methyl, ethyl, isopropyl, dimethyl, allyl or phenyl. The hydrogen atom to be substituted may be 1 or 2 or more.
The content of the structural unit having an electron donating group in the polyvinyl acetal resin is preferably limited to 0.01 mol% at the lower end and 10 mol% at the upper end. The adhesiveness can be improved by setting the content to 0.01 mol% or more, and the viscosity can be prevented from rising by setting the content to 10 mol% or less. The lower limit of the above content is more preferably 0.05 mol%, and the upper limit is more preferably 8 mol%. The upper limit is more preferably 6 mol%.
The polyvinyl acetal resin has an electron withdrawing group.
The above electron withdrawing group preferably has an acid dissociation constant (pKa) in water of less than 25.
By making the pKa smaller than 25, electrons can be efficiently received. More preferably, the pKa is less than 20. The pKa is preferably 1.0 or more.
The pKa of the electron withdrawing group may be measured by a potentiometric method or a neutralization titration method.
The bonding position of the electron withdrawing group is not particularly limited, and may be directly bonded to the main chain carbon or may be bonded via a linking group. In addition, the structure may be bonded to an acetal group. Further, the graft chain having an electron withdrawing group may be bonded to the end of the resin, or the electron withdrawing group may be bonded to the end of the resin. Among them, a structure directly bonded to the main chain carbon and a structure bonded to the main chain carbon via a linking group are preferable.
Examples of the electron-withdrawing group include acidic groups such as carboxyl group, phosphate group, boric acid and borate, and nitro group (-NO) 2 ) Examples of the sulfur-containing group include a nitrogen-containing group such as an amide group and a nitrile group, a sulfo group, a sulfonyl group and a sulfinyl group, and a formyl group (-CHO), a fluoroalkyl group, a halogen group and the like.
Among them, carboxyl groups are preferable.
The content of the structural unit having an electron withdrawing group in the polyvinyl acetal resin is preferably limited to 0.01 mol% at the lower end and 10 mol% at the upper end. When the content is not less than 0.01 mol%, dispersibility of the active material and the conductive additive can be improved, and when the content is not more than 10 mol%, an increase in viscosity can be prevented. The lower limit of the above content is more preferably 0.05 mol%, and the upper limit is more preferably 8 mol%. The upper limit is more preferably 6 mol%.
The ratio of the content of the structural unit having an electron withdrawing group to the content of the structural unit having an electron donating group (content of the structural unit having an electron withdrawing group/content of the structural unit having an electron donating group) in the polyvinyl acetal resin is preferably 0.001 to 1000. When the amount is within the above range, electron conductivity can be improved and resistance can be suppressed. Preferably 0.01 to 100.
The difference between the acid dissociation constant of the electron donating group and the acid dissociation constant of the electron withdrawing group (the acid dissociation constant of the electron withdrawing group—the acid dissociation constant of the electron donating group) in the polyvinyl acetal resin is preferably 1.0 to 20. When the amount is within the above range, electron conductivity can be improved and resistance can be suppressed. Preferably 1.5 to 15.0.
In addition, the ratio of the content of the structural unit having an electron withdrawing group to the amount of hydroxyl groups (content of the structural unit having an electron donating group/amount of hydroxyl groups) in the polyvinyl acetal resin is preferably 1.00×10 -4 ～4.5×10 -1 . By setting the range to the above range, electrons can be efficiently transferred and received, and the conductivity can be improved.
The polyvinyl acetal resin includes a structural unit having an acetal group.
The content (acetalization degree) of the structural unit having an acetal group in the polyvinyl acetal resin is preferably 20 to 70 mol%. The acetalization degree is set to 20 mol% or more, whereby the solubility in a solvent is improved, and the composition can be suitably used. When the acetalization degree is 70 mol% or less, the resistance to the electrolyte becomes sufficient, and the dissolution of the resin component into the electrolyte can be prevented when the electrode is immersed in the electrolyte. More preferably 40 to 65 mol%. More preferably 45 to 65 mol%.
In the present specification, the acetalization degree means: the proportion of hydroxyl groups of polyvinyl alcohol that are acetalized with butyraldehyde. In addition, since the acetalization group of the polyvinyl acetal resin is formed by acetalization of 2 hydroxyl groups, the method of counting the acetalized 2 hydroxyl groups is employed to calculate the mol% of the acetalization degree.
In the present specification, the acetalization degree means a content of a structural unit having an acetal group relative to the entire polyvinyl acetal resin.
The above structural unit having an acetal group is obtained by acetalization with an aldehyde.
The lower limit of the carbon number of the aldehyde (carbon number excluding aldehyde groups) is preferably 1, and the upper limit is preferably 11. When the carbon number is within the above range, the hydrophobicity of the resin becomes low, and thus the purification efficiency is improved, and the Na ion content can be reduced.
Specific examples of the aldehyde include aldehydes having a vinyl group (vinyl aldehyde) such as acetaldehyde, butyraldehyde, benzaldehyde, propionaldehyde, and acrolein.
Further, the acetal group is preferably at least 1 selected from the group consisting of a butyral group, a benzaldehyde group, an acetal group, a propionaldehyde group and a vinylacetal group.
In the polyvinyl acetal resin, the ratio of the acetalized portion with acetaldehyde to the acetalized portion with butyraldehyde is preferably 0/100 to 50/50. Thus, the polyvinyl acetal resin becomes soft, and the adhesion to the current collector becomes good. The ratio of the acetalized portion with acetaldehyde to the acetalized portion with butyraldehyde is more preferably 0/100 to 20/80.
The polyvinyl acetal resin contains a structural unit having a hydroxyl group.
The lower limit of the content of the structural unit having a hydroxyl group (hydroxyl group amount) in the polyvinyl acetal resin is 35 mol% and the upper limit thereof is 70 mol%. When the hydroxyl group content is 35 mol% or more, the resistance to the electrolyte is improved, and the dissolution of the resin into the electrolyte can be prevented, and when 70 mol% or less, the flexibility of the resin is improved, and the adhesion to the current collector is sufficient.
The preferable lower limit of the amount of the hydroxyl groups is 40 mol%, and the preferable upper limit is 65 mol%. More preferably, the lower limit is 45 mol%, and still more preferably, the upper limit is 60 mol%.
In the present specification, the hydroxyl group amount means the content of the structural unit having a hydroxyl group relative to the entire polyvinyl acetal resin.
The polyvinyl acetal resin preferably contains a structural unit having an acetyl group.
The content of the structural unit having an acetyl group (acetyl group amount) in the polyvinyl acetal resin is preferably limited to 0.1 mol% at the lower end and 15 mol% at the upper end. When the amount of the acetyl group is 0.1 mol% or more, flexibility of the resin is improved, adhesion to the current collector can be made sufficient, and when the amount of the acetyl group is 15 mol% or less, resistance to the electrolyte is improved, and elution to the electrolyte to cause a short circuit can be prevented. The lower limit of the amount of the acetyl group is more preferably 1 mol%, and the upper limit is more preferably 10 mol%.
In the present specification, the amount of acetyl groups refers to the content of structural units having acetyl groups relative to the entire polyvinyl acetal resin.
In the polyvinyl acetal resin, the ratio of the content of the structural unit having an electron donating group to the content of the structural unit having a hydroxyl group (content of the structural unit having an electron donating group/content of the structural unit having a hydroxyl group) is preferably 0.0001 to 1.50. When the amount is within the above range, the resistance value of the composition for a secondary battery electrode can be suppressed.
More preferably 0.01 to 0.89, still more preferably 0.01 to 0.43.
The lower limit of the polymerization degree of the polyvinyl acetal resin is 250 and the upper limit is 800. The polymerization degree is set to 250 or more, and thus the industrial availability is easy. By setting the polymerization degree to 800 or less, the solution viscosity is reduced, and the active material can be sufficiently dispersed. The preferable lower limit of the polymerization degree is 280, and the preferable upper limit is 600.
In the present invention, the term "a polyvinyl acetal resin having an electron donating group and an electron withdrawing group" means: in addition to the case of having an electron donating group and an electron withdrawing group in the same polyvinyl acetal resin, the case of having an electron donating group and an electron withdrawing group in different polyvinyl acetal resins is also included. In the case where different polyvinyl acetal resins have an electron donating group and an electron withdrawing group, the "polymerization degree of the polyvinyl acetal resin" means a polymerization degree calculated by distributing the polymerization degrees of the respective resins in accordance with a mixing ratio.
The content of the polyvinyl acetal resin in the composition for a secondary battery electrode of the invention is not particularly limited, but the lower limit is preferably 0.2 wt% and the upper limit is preferably 5 wt%. The adhesion to the current collector can be improved by setting the content of the polyvinyl acetal resin to 0.2 wt% or more, and the discharge capacity of the secondary battery can be improved by setting the content to 5 wt% or less. More preferably 0.5 to 3% by weight.
The polyvinyl acetal resin is produced by acetalizing polyvinyl alcohol with aldehyde.
In particular, as a method for producing the polyvinyl acetal resin, there is mentioned: a method of preparing a polyvinyl alcohol having the electron donating group and the electron withdrawing group, and then acetalizing the polyvinyl alcohol; and a method in which the electron donating group and the electron withdrawing group are added after acetalizing the polyvinyl alcohol having no electron donating group and no electron withdrawing group.
Alternatively, a method may be used in which a mixed polyvinyl alcohol containing the polyvinyl alcohol having an electron donating group and the polyvinyl alcohol having an electron withdrawing group is prepared and then acetalized.
Examples of the method for producing the polyvinyl alcohol having the electron donating group and the electron withdrawing group include a method in which a monomer having an electron donating group and a monomer having an electron withdrawing group are copolymerized with a vinyl ester such as vinyl acetate, and then an acid or a base is added to an alcoholic solution of the resulting copolymer to effect saponification.
Examples of the monomer containing an electron donating group include monomers containing a lactam group.
Examples of the monomer containing a lactam group include N-vinyl-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-pyrrolidone, and N-vinyl-3-methyl-2-piperidone. Further, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2-pyrrolidone, and the like can be mentioned. Further, N-vinyl-5-methyl-2-piperidone, N-vinyl-5-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4, 5-dimethyl-2-pyrrolidone, N-vinyl-3, 5-trimethyl-2-pyrrolidone, and the like can be mentioned.
Examples of the method of adding the electron donating group and the electron withdrawing group include a method of reacting a polyvinyl acetal resin having no electron donating group and no electron withdrawing group with a monomer having an electron donating group, a monomer having an electron withdrawing group, and the like.
The polyvinyl alcohol having no electron donating group and no electron withdrawing group as described above can be obtained, for example, by saponifying a copolymer of vinyl ester and ethylene. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl pivalate. Among them, vinyl acetate is preferable from the viewpoint of economy.
The composition for a secondary battery electrode of the present invention may further contain a polyvinylidene fluoride resin in addition to the polyvinyl acetal resin.
By using the polyvinylidene fluoride resin in combination, the resistance to the electrolyte is further improved, and the discharge capacity can be improved.
When the polyvinylidene fluoride resin is contained, the weight ratio of the polyvinyl acetal resin to the polyvinylidene fluoride resin is preferably 0.5:9.5 to 7:3.
By setting the range to such a value, the current collector can have significantly insufficient adhesion to the current collector, and resistance to the electrolyte can be provided.
The weight ratio of the polyvinyl acetal resin to the polyvinylidene fluoride resin is more preferably 1:9 to 4:6.
In the composition for a secondary battery electrode of the present invention, the content of the polyvinyl acetal resin is preferably limited to 0.01 part by weight, and the upper limit is preferably limited to 20 parts by weight, based on 100 parts by weight of the active material. The adhesion to the current collector can be improved by setting the content of the polyvinyl acetal resin to 0.01 part by weight or more, and the discharge capacity of the secondary battery can be improved by setting the content to 20 parts by weight or less.
In the composition for a secondary battery electrode of the present invention, the content of the polyvinyl acetal resin is preferably limited to 0.01 part by weight, and the upper limit is preferably limited to 200 parts by weight, based on 100 parts by weight of the conductive auxiliary agent.
The content of the binder in the composition for a secondary battery electrode of the present invention is not particularly limited, but the lower limit is preferably 1 wt% and the upper limit is preferably 30 wt%. The binder content is 1 wt% or more, whereby the adhesion to the current collector can be improved, and the discharge capacity of the secondary battery can be improved by 30 wt% or less.
The composition for a secondary battery electrode of the present invention contains an organic solvent.
The organic solvent is not particularly limited as long as it can dissolve the polyvinyl acetal resin, and examples thereof include cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, isopropyl alcohol, N-methylpyrrolidone, ethanol, distilled water, and the like. Among them, N-methylpyrrolidone is preferable.
The organic solvents may be used alone or in combination of 2 or more.
The content of the organic solvent in the composition for a secondary battery electrode of the present invention is not particularly limited, but the lower limit is preferably 20% by weight, and the upper limit is preferably 50% by weight. By setting the content of the organic solvent to 20% by weight or more, the viscosity can be reduced, the paste can be easily applied, and by setting the content to 50% by weight or less, the occurrence of unevenness in the solvent during drying can be prevented. The lower limit is more preferably 25% by weight, and the upper limit is more preferably 40% by weight.
In the composition for a secondary battery electrode of the present invention, additives such as a flame retardant aid, a thickener, a defoaming agent, a leveling agent, and an adhesion imparting agent may be added as required in addition to the active material, the polyvinyl acetal resin, and the organic solvent.
The method for producing the composition for a secondary battery electrode of the present invention is not particularly limited, and examples thereof include a method in which the active material, a binder containing a polyvinyl acetal resin, an organic solvent, and various additives added as needed are mixed using various mixers such as a planetary mixer, a disperser, a ball mill, a blending mill, and a three-roll mill.
The composition for a secondary battery electrode of the present invention is formed into an electrode, for example, through a process of coating onto a conductive substrate and drying.
A secondary battery using the composition for a secondary battery electrode of the present invention is also one of the present invention.
Examples of the secondary battery include nickel-cadmium batteries, nickel-hydrogen batteries, lithium secondary batteries, all-solid-state batteries, and fuel cells. Among them, a lithium secondary battery is preferable.
As a coating method for coating the composition for a secondary battery electrode of the present invention onto a conductive substrate, various coating methods typified by, for example, an extrusion coater, a dip coater, a spin coater, a counter roll, a doctor blade, an applicator, and the like can be employed.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a composition for a secondary battery electrode is provided which has excellent dispersibility and adhesiveness of an active material, can prevent deterioration and failure of a battery due to moisture absorption, and can produce a high-capacity secondary battery. The composition for a secondary battery electrode of the present invention is excellent in viscosity, and can prevent decomposition or degradation when a voltage is applied to the electrode, thereby enabling the production of a secondary battery electrode having high flexibility.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(Synthesis of polyvinyl acetal resin A)
To 3000 parts by weight of pure water, 350 parts by weight of polyvinyl alcohol (polymerization degree 250 and saponification degree 98.3 mol%) containing a structural unit having an electron donating group (lactam structure represented by the following formula (2), n=1 in the formula (1) and a structural unit having an electron withdrawing group (carboxyl group) was added, and stirred at 90 ℃ for about 2 hours, and dissolved. The content of the structural unit having a lactam structure represented by the following formula (2) [ electron donating group amount ] in the polyvinyl alcohol was 0.01 mol%, and the content of the structural unit having a carboxyl group [ electron withdrawing group amount ] was 10 mol%.
After cooling the solution to 40℃and adding 230 parts of 35% strength by weight hydrochloric acid thereto, the liquid temperature was lowered to 5℃and 53.1 parts by weight of n-butyraldehyde was added thereto, and the acetalation reaction was carried out while maintaining the temperature, whereby the reaction product was precipitated. Thereafter, the reaction was completed by maintaining the liquid temperature at 30℃for 3 hours, and a white powder of the polyvinyl acetal resin was obtained by neutralization, washing with water and drying by a conventional method.
The amount of hydroxyl groups, the degree of acetalization, the amount of electron-withdrawing groups, and the amount of electron-donating groups were measured with respect to the obtained polyvinyl acetal resin a by using FT-IR, and as a result, the amount of hydroxyl groups was 35.2 mol%, the degree of acetalization (degree of butyralization) was 53.1 mol%, the amount of acetyl groups was 1.7 mol%, the amount of electron-donating groups was 0.01 mol%, and the amount of electron-withdrawing groups was 10 mol%.
(Synthesis of polyvinyl Acetal resin B-I, L-O, Q-V, Y1-4)
The polyvinyl acetal resins B to I, L to O, Q to V, Y1 to 4 were synthesized in the same manner as the polyvinyl acetal resin a except that the polyvinyl alcohol (type) and aldehyde (amount) shown in table 1 were used.
(Synthesis of polyvinyl acetal resin J1)
The polyvinyl acetal resin J1 was synthesized in the same manner as the polyvinyl acetal resin a except that polyvinyl alcohol J1 (polymerization degree: 400 and saponification degree: 98.3 mol%) was used instead of polyvinyl alcohol a and aldehyde (addition amount) shown in table 1 was used. In the polyvinyl alcohol J1, the content of the structural unit having an amino group [ the amount of an electron donating group ] was 0.1 mol%, and the content of the structural unit having a sulfo group [ the amount of an electron withdrawing group ] was 0.1 mol%.
(Synthesis of polyvinyl acetal resin J2)
The polyvinyl acetal resin J2 was synthesized in the same manner as the polyvinyl acetal resin a except that polyvinyl alcohol J2 (polymerization degree: 400 and saponification degree: 98.1 mol%) was used instead of polyvinyl alcohol a and aldehyde (addition amount) shown in table 1 was used. In the polyvinyl alcohol J2, the content [ electron donating group amount ] of the lactam structure [ n=3 in the formula (1), pyrrolidone modification ] was 0.1 mol%, and the content [ electron withdrawing group amount ] of the structural unit having a carboxyl group was 0.1 mol%.
(Synthesis of polyvinyl acetal resin J3)
The polyvinyl acetal resin J3 was synthesized in the same manner as the polyvinyl acetal resin a except that polyvinyl alcohol J3 (polymerization degree: 800 and saponification degree: 98.4 mol%) was used instead of polyvinyl alcohol a and aldehyde (addition amount) shown in table 1 was used. In the polyvinyl alcohol J3, the content of the structural unit having the lactam structure represented by the above formula (2) [ electron donating group amount ] was 0.1 mol%, and the content of the structural unit having the amide group [ electron withdrawing group amount ] was 0.1 mol%.
(Synthesis of polyvinyl Acetal resin K, P)
Instead of polyvinyl alcohol A, a mixed polyvinyl alcohol K obtained by mixing a polyvinyl alcohol having a structural unit having an electron-donating group (lactam structure represented by the above formula (2)) with a polyvinyl alcohol having a structural unit having an electron-withdrawing group (carboxyl group) in a ratio of 1:1 is used. The polyvinyl acetal resin K was synthesized in the same manner as the polyvinyl acetal resin a except that the aldehyde (addition amount) shown in table 1 was used.
In the case of polyvinyl alcohol containing a structural unit having an electron donating group (a lactam structure represented by the above formula (2)), the polymerization degree was 600, the saponification degree was 97.8 mol%, and the content of the structural unit having the lactam structure represented by the above formula (2) [ amount of electron donating group ] was 0.2 mol%.
Further, in the case of polyvinyl alcohol containing a structural unit having an electron withdrawing group (carboxyl group), the degree of polymerization was 200, the degree of saponification was 97.3 mol%, and the content of the structural unit having a carboxyl group [ amount of electron withdrawing group ] was 0.2 mol%.
Similarly, a polyvinyl acetal resin P was synthesized in the same manner as in the polyvinyl acetal resin a except that a mixed polyvinyl alcohol P was used and the aldehyde (addition amount) shown in table 1 was used.
(Synthesis of polyvinyl acetal resin W)
A polyvinyl acetal resin W was synthesized in the same manner as the polyvinyl acetal resin a except that polyvinyl alcohol W (polymerization degree: 400, saponification degree: 98.4 mol%, content of structural unit having methyl group [ electron donating group amount ] was 0.1 mol%) was used instead of polyvinyl alcohol a, and aldehyde (addition amount) shown in table 1 was used.
(Synthesis of polyvinyl acetal resin X)
Instead of polyvinyl alcohol a, a mixed polyvinyl alcohol X obtained by mixing a polyvinyl alcohol having a structural unit having an electron-withdrawing group (methyl) with a polyvinyl alcohol having a structural unit having an electron-withdrawing group (carboxyl) in a ratio of 1:1 is used. The polyvinyl acetal resin X was synthesized in the same manner as the polyvinyl acetal resin a except that the aldehyde (addition amount) shown in table 1 was used.
In the case of polyvinyl alcohol containing a structural unit having an electron donating group (methyl group), the polymerization degree was 600, the saponification degree was 98.3 mol%, and the content of the structural unit having a methyl group [ electron donating group amount ] was 0.2 mol%.
Further, in the case of polyvinyl alcohol containing a structural unit having an electron withdrawing group (carboxyl group), the polymerization degree was 200, the saponification degree was 98.2 mol%, and the content of the structural unit having a carboxyl group [ amount of electron withdrawing group ] was 0.2 mol%.
Example 1
(preparation of composition for Secondary Battery electrode)
To 20 parts by weight of a resin solution containing the obtained polyvinyl acetal resin A (polyvinyl acetal resin: 2.5 parts by weight), 50 parts by weight of lithium cobaltate (manufactured by Japanese chemical industry Co., ltd., CELLSEED C-5H), 5 parts by weight of acetylene BLACK (manufactured by electric chemical industry Co., ltd., DENKA BLACK) as a conductive additive, and 26 parts by weight of N-methylpyrrolidone were added as active materials. Then, the resulting mixture was mixed with a defoaming device made by THINKY to obtain a composition for a secondary battery electrode.
Examples 2 to 18 and comparative examples 1 to 3 and 5 to 12
A composition for a secondary battery electrode was obtained in the same manner as in example 1, except that the polyvinyl acetal resin (type of resin, addition amount) shown in table 2 was used.
Comparative example 4
A composition for a secondary battery electrode was obtained in the same manner as in example 1, except that the polyvinyl acetal resins T1 and T2 shown in table 1 were mixed and used.
TABLE 1
In the "functional group type" in table 1, a represents a functional group (aziridinyl) having a lactam structure, b represents an amino group, c represents a functional group (pyrrolidone group) having a lactam structure, d represents an amide group, e represents a methyl group, p represents a carboxyl group, and q represents a sulfo group. B, d, e, p, q each has a structure in which each functional group is directly bonded to a carbon of the main chain.
< evaluation >
The secondary battery electrode compositions obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 2. In each example and comparative example, the white powder obtained properly for the polyvinyl acetal resin was evaluated as "o", and the white powder obtained improperly due to the occurrence of particle adhesion was evaluated as "x" (resin powdering evaluation).
(1) Adhesiveness (peeling force)
The compositions for secondary battery electrodes obtained in examples and comparative examples were evaluated for adhesion to aluminum foil.
The electrode composition was coated on an aluminum foil (thickness: 20 μm) so that the film thickness after drying became 20 μm, and dried to obtain a test piece having a sheet-like electrode formed on the aluminum foil.
The sample was cut into 1cm in the vertical direction and 2cm in the horizontal direction, and the electrode sheet was pulled up while fixing the test piece using AUTOGRAPH (manufactured by Shimadzu corporation, "AGS-J"), and the peeling force (N) required until the electrode sheet was completely peeled off from the aluminum foil was measured, and then, the sample was evaluated according to the following criteria.
O: peel force of greater than 8.0N
Delta: the stripping force is 5.0 to 8.0N
X: peel force of less than 5.0N
(2) Dispersibility (surface roughness)
The surface roughness Ra of the test piece obtained in the above "(1) adhesiveness" was measured based on JIS B0601 (1994), and the surface roughness of the electrode was evaluated according to the following criteria. In general, it is said that: the higher the dispersibility of the active material, the smaller the surface roughness becomes.
O: ra is less than 3 mu m
Delta: ra is 3 μm or more and less than 4 μm
X: ra is above 4 μm
(3) Electrolyte resistance (solvent solubility)
(production of electrode sheet)
The compositions for secondary battery electrodes obtained in examples and comparative examples were applied to a release-treated polyethylene terephthalate (PET) film so that the film thickness after drying became 20 μm, and dried to produce electrode sheets.
The electrode sheet was cut into 2cm square pieces to prepare an electrode sheet test piece.
(evaluation of dissolution Rate)
The weight of the obtained test piece was accurately measured, and the weight of the resin contained in the test piece was calculated from the weight ratio of the components contained in the piece. Thereafter, the test piece was put into a bag-like net, and the total weight of the net bag and the test piece was accurately measured.
Next, the mesh bag containing the test piece was immersed in a mixed solvent of diethyl carbonate/ethylene carbonate=1:1 as an electrolyte solvent, and left at 60 ℃ for 5 hours. After leaving, the mesh bag was taken out, and dried at 150℃for 8 hours to completely dry the solvent.
After removal from the dryer, the mixture was left at room temperature for 1 hour, and the weight was measured. The resin elution amount was calculated from the weight change before and after the test, and the resin elution rate was calculated from the ratio of the resin elution amount to the weight of the resin calculated in advance, and was evaluated according to the following criteria.
O: the dissolution rate is less than 1%
Delta: the dissolution rate is more than 1% and less than 2%
X: the dissolution rate is more than 2 percent
(4) Hygroscopicity
The weight of the test piece obtained in the above "(3) electrolyte resistance" was accurately measured.
Thereafter, the test piece was left to stand at a relative humidity of 95% at 30℃for 24 hours. After taking out, the weight of the test piece was accurately measured. The water content was calculated from the weight change before and after the test, and evaluated according to the following criteria.
O: the water content is less than 5%
Delta: the water content is more than 5% and less than 7%
X: the water content is above 7%
(5) Electrode resistance measurement
The electrode sheet obtained in the above "(1) adhesiveness" was evaluated according to the following criteria by measuring the electrode resistance value using an electrode resistance measuring device (manufactured by daily electric motor company).
O: the electrode resistance value is less than 1000 omega/sq
X: the resistance value of the electrode is above 1000 ohm/sq
TABLE 2
Industrial applicability
According to the present invention, a composition for a secondary battery electrode is provided which has excellent dispersibility and adhesiveness of an active material, can prevent deterioration and failure of a battery due to moisture absorption, and can produce a high-capacity secondary battery.
Claims (14)
1. A composition for a secondary battery electrode, characterized in that it contains an active material, a binder and an organic solvent,
the binder contains a polyvinyl acetal resin,
the polyvinyl acetal resin has an electron-withdrawing group and an electron-donating group having an acid dissociation constant in water of less than 16, and has a degree of polymerization of 250 to 800 and a hydroxyl group amount of 35 to 70 mol%,
the electron donating group is at least 1 selected from the group consisting of amino, alkylamino, -S-, and functional groups having a lactam structure,
the electron withdrawing group is at least 1 selected from acid groups, nitro groups, amide groups, nitrile groups, sulfo groups, sulfonyl groups, sulfinyl groups, formyl groups, fluoroalkyl groups and halogen,
the lactam structure is at least 1 cyclic structure selected from the group consisting of a three-membered ring, a four-membered ring, a five-membered ring and a six-membered ring.
2. The composition for a secondary battery electrode according to claim 1, wherein the electron donating group is a functional group having a lactam structure.
3. The composition for a secondary battery electrode according to claim 1 or 2, wherein the lactam structure is a structure represented by the following formula (1),
in the formula (1), n represents an integer of 1 to 5, R 1 Represents a single bond or a saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms.
4. The composition for a secondary battery electrode according to claim 1 or 2, wherein the hydrocarbon constituting the cyclic structure of the lactam structure is unsubstituted or the hydrogen atom is substituted with a saturated hydrocarbon or an unsaturated hydrocarbon having 1 to 10 carbon atoms.
5. The composition for a secondary battery electrode according to claim 1 or 2, wherein the content of the structural unit having an electron donating group in the polyvinyl acetal resin is 0.01 mol% to 10 mol%.
6. The composition for a secondary battery electrode according to claim 1 or 2, wherein the electron withdrawing group is at least 1 selected from the group consisting of an acidic group, a nitro group, a sulfo group, a sulfonyl group, a sulfinyl group, a formyl group, a fluoroalkyl group, and a halogen.
7. The composition for a secondary battery electrode according to claim 1 or 2, wherein the electron withdrawing group is a structure directly bonded to a main chain carbon or a structure bonded to an acetal group.
8. The composition for a secondary battery electrode according to claim 1, wherein the electron withdrawing group is a carboxyl group.
9. The composition for a secondary battery electrode according to claim 1 or 8, wherein the content of the structural unit having an electron withdrawing group in the polyvinyl acetal resin is 0.01 mol% to 10 mol%.
10. The composition for a secondary battery electrode according to claim 1 or 2, wherein the degree of acetalization of the polyvinyl acetal resin is 20 mol% to 70 mol%.
11. The composition for a secondary battery electrode according to claim 1 or 2, wherein the amount of acetyl groups of the polyvinyl acetal resin is 15 mol% or less.
12. The composition for a secondary battery electrode according to claim 1 or 2, wherein the composition contains 0.01 to 20 parts by weight of the polyvinyl acetal resin per 100 parts by weight of the active material.
13. The composition for a secondary battery electrode according to claim 1 or 2, further comprising a polyvinylidene fluoride resin.
14. A secondary battery, characterized in that it is produced using the composition for a secondary battery electrode according to claim 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12 or 13.
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| CN103124766A (en) * | 2010-09-29 | 2013-05-29 | 积水化学工业株式会社 | Method for producing slurry composition |
| JP2016076374A (en) * | 2014-10-06 | 2016-05-12 | 積水化学工業株式会社 | Composition for lithium secondary battery electrode |
| CN105659419A (en) * | 2014-03-27 | 2016-06-08 | 积水化学工业株式会社 | Binder for power storage device electrode |
| CN107210445A (en) * | 2015-09-17 | 2017-09-26 | 积水化学工业株式会社 | Electrical storage device electrode binding agent |
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| JP5827581B2 (en) * | 2011-02-28 | 2015-12-02 | 積水化学工業株式会社 | Lithium secondary battery electrode composition |
| JP5670286B2 (en) * | 2011-09-20 | 2015-02-18 | 株式会社クラレ | Battery electrode and lithium ion secondary battery using the same |
| JP6044773B2 (en) | 2012-01-30 | 2016-12-14 | 日本ゼオン株式会社 | Secondary battery positive electrode binder composition, secondary battery positive electrode slurry composition, secondary battery positive electrode and secondary battery |
| CN105531854B (en) | 2013-09-24 | 2017-10-31 | 东洋油墨Sc控股株式会社 | Non-aqueous secondary batteries adhesive, non-aqueous secondary batteries resin combination, non-aqueous secondary batteries barrier film, non-aqueous secondary batteries electrode and non-aqueous secondary batteries |
| JP6255260B2 (en) | 2014-01-30 | 2017-12-27 | 積水化学工業株式会社 | Lithium secondary battery electrode composition |
| JP6445774B2 (en) * | 2014-03-31 | 2018-12-26 | 積水化学工業株式会社 | Modified polyvinyl acetal resin |
| JP6654844B2 (en) * | 2014-10-08 | 2020-02-26 | 積水化学工業株式会社 | Composition for lithium secondary battery electrode |
| JP6943707B2 (en) * | 2016-08-23 | 2021-10-06 | 積水化学工業株式会社 | Water-soluble resin composition and water-soluble resin film |
| JP7107645B2 (en) * | 2016-09-30 | 2022-07-27 | 積水化学工業株式会社 | Composition for secondary battery electrode |
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| CN103124766A (en) * | 2010-09-29 | 2013-05-29 | 积水化学工业株式会社 | Method for producing slurry composition |
| CN105659419A (en) * | 2014-03-27 | 2016-06-08 | 积水化学工业株式会社 | Binder for power storage device electrode |
| JP2016076374A (en) * | 2014-10-06 | 2016-05-12 | 積水化学工業株式会社 | Composition for lithium secondary battery electrode |
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